EP2513184B1 - Production of epoxy resins using improved ion exchange resin catalysts - Google Patents

Production of epoxy resins using improved ion exchange resin catalysts Download PDF

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Publication number
EP2513184B1
EP2513184B1 EP10798211.8A EP10798211A EP2513184B1 EP 2513184 B1 EP2513184 B1 EP 2513184B1 EP 10798211 A EP10798211 A EP 10798211A EP 2513184 B1 EP2513184 B1 EP 2513184B1
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European Patent Office
Prior art keywords
anion exchange
exchange resin
percent
functionalized
resin
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EP10798211.8A
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German (de)
English (en)
French (fr)
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EP2513184A1 (en
Inventor
Philip Carlberg
H. Goltz
Leming Gu
William Harris
David West
William Worley
Thomas Young
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • This invention relates generally to production of an epoxy resin, especially a liquid epoxy resin, using an ion exchange resin catalyst, especially an improved or modified anion exchange resin such as a functionalized, quaternary amine anion exchange resin as described more fully below.
  • a first approach accomplishes the two reactions simultaneously, typically by adding an aqueous inorganic hydroxide mixture (usually 20 percent by weight (wt%) to 50 wt% sodium hydroxide (NaOH)) to an organic mixture containing the polyhydric phenol and the epihalohydrin.
  • a catalyst to etherify (couple) the polyhydric phenol and the epihalohydrin to produce the bishalohydrin ether, and then, sequentially, effect the dehalohydrogenation (epoxidation) reaction by adding the aqueous inorganic hydroxide mixture to an organic mixture containing the bishalohydrin ether and an organic solvent (e.g. excess epihalohydrin).
  • an organic solvent e.g. excess epihalohydrin
  • the first approach used more often than the second approach, employs a plurality of batch reactors and excess epihalohydrin in the organic mixture.
  • One may leave water in the reactor to form a two-phase mixture or remove it by azeotropic distillation to precipitate inorganic halide salt.
  • limitations on maximum size of the reactors means that a large facility will contain multiple batch reactors, thereby increasing facility cost.
  • the second, less frequently used, approach uses any of a number of previously-identified etherification (coupling) catalysts such as quaternary ammonium or phosphonium halides, hydroxides, carbonates and carboxylates, alkali metal or alkaline earth halides, carbonates, hydroxides and carbonates, sulfonium halides, tertiary amines, tertiary phosphines, organic sulfides, tertiary ammonium alkylides, tertiary phosphonium alkylides, betaines and Lewis acids.
  • etherification (coupling) catalysts such as quaternary ammonium or phosphonium halides, hydroxides, carbonates and carboxylates, alkali metal or alkaline earth halides, carbonates, hydroxides and carbonates, sulfonium halides, tertiary amines, tertiary phosphines, organic sulfides
  • hydroxides, tertiary amines, tertiary phosphines, and carboxylates function as both a catalyst and a reactant and are consumed during the reaction.
  • Some catalysts e.g. tertiary amines and tertiary phosphines
  • Some catalysts also initiate an irreversible reaction between the epihalohydrin or the epoxy resin, forming undesirable adducts of the catalyst that cannot easily be removed from the epoxy resin.
  • Some catalysts e.g. Lewis acids
  • Some suffer from poor selectivity, giving undesirable product quality.
  • Some (e.g. inorganic halides) have very low solubility in the epihalohydrin/phenol mixture and thus either cannot easily catalyze the reaction or otherwise give only very low catalytic activity.
  • United States Patent (US) 3,176,027 and British Patent (GB) 888,945 describe production of glycidyl ethers of monohydric phenols or polyhydric phenols by reacting a phenol with a haloepoxyalkane (epihalohydrin) in the presence of high-molecular-weight catalysts that are insoluble in the reaction medium.
  • the catalysts contain polar groups, where the polar groups are either (i) salt-like groups, (ii) groups capable of forming salt-like groups in the reaction mixture or (iii) acid amide groups.
  • the catalyst may be an anion exchange resin that contains an amino, quaternary ammonium, quaternary phosphonium or ternary sulfonium group.
  • DowexTM 1X10 is a quaternary amine styrene-divinylbenzene type anion exchange resin
  • LewatitTM MN is described as being a strongly basic polycondensate which contains quaternary amine groups.
  • GB 1,159,530 , US 3,925,407 and US 4,014,824 teach that quaternary ammonium anion exchange resins can be used to catalyze the etherification reaction between a phenol, an aliphatic alcohol or an amine and an epihalohydrin.
  • US 3,372,142 provides an example using a "strong anion exchange resin" to catalyze the reaction between epichlorohydrin and phenol.
  • Cipheral Patent Publication (CN) 1,931,890 discusses preparation of dried quaternary ammonium exchange resins, treated to contain only hydroxide anions. It also describes a batch procedure that uses the treated anion exchange resins as catalysts and reactants for the etherification and dehydrohalogenation of bisphenol-A and epichlorohydrin to produce a liquid epoxy resin.
  • CN 1,546,548 teaches preparation of low-molecular weight bisphenol-A epoxy resin using either carbonate salts or anion exchange resins as catalysts.
  • the teachings include a batch procedure in which bisphenol-A, epichlorohydrin and either carbonate salts or anion exchange resins in the hydroxide form are combined and reacted for 3-10 hours at 60-110 deg C, followed by filtration and devolatilization.
  • CN 1,941,890 and CN 1,546,548 both provide for use of anion exchange resins in the hydroxide form as a replacement for sodium hydroxide in batch caustic coupling and epoxidation reactions to make bisphenol-A liquid epoxy resins. Used this way, the ion exchange resins are reactants, not catalysts.
  • this invention is an improved process for producing a liquid epoxy resin by etherifying a polyhydric phenol and an epihalohydrin with an amine-functionalized anion exchange resin as a catalyst to produce a bishalohydrin ether and dehydrohalogenating the bishalohydrin ether with an aqueous inorganic hydroxide mixture, the bishalohydrin ether optionally being in admixture with an organic solvent, wherein the improvement comprises using a modified amine-functionalized anion exchange resin as an etherification catalyst, the modified amine-functionalized anion exchange resin having at least one of a) a polymerized crosslinking monomer content within a range of from 0.1 percent by weight (wt%) to 4 wt%, each percent by weight being based upon total weight of the monomers used to prepare the anion exchange resin copolymer, b) an average particle size within a range of from 10 micrometers ( ⁇ m) to 200 ⁇ m, c) a degree of functionalization such that from 2
  • Anion exchange resins suitable for use in this invention include any ion exchange resin comprising a cation bound to a crosslinked polymer, which can exchange anions.
  • suitable anion exchange resins include chloromethylated crosslinked polystyrene quaternized with tertiary amines, crosslinked polyacrylates quaternized with polyamines containing quaternary amine groups, quaternized crosslinked polyvinylpylidine and resins prepared by copolymerizing vinylbenzylchloride, divinylbenzene and, optionally, a third monomer selected from styrene, alkylstyrenics, acrylates and methacrylates.
  • Suitable anion exchange resins may also be prepared by functionalization of chloromethylated crosslinked polystyrene with quaternary phosphonium or tertiary sulfonium groups. Chloromethylated crosslinked polystyrene quaternized with tertiary amines are preferred.
  • the anion exchange resin may be either gel type or macroporous.
  • crosslinking monomers examples include polyvinylidene aromatics such as divinylbenzene, divinyltoluene, divinylxylene, divinylnaphthalene, trivinylbenzene, bis(vinylphenyl)alkanes, divinyldiphenylsulfone, as well as diverse alkylene diacrylates and alkylene dimethacrylates.
  • Preferred crosslinking monomers are divinylbenzene, trivinylbenzene, and bis(vinylphenyl)ethane.
  • crosslinking agent crosslinker
  • crosslinking monomer are used herein as synonyms and are intended to include both a single species of crosslinking agent along with combinations of different types of crosslinking agents
  • R 1 , R 2 and R 3 are each independently selected from: alkyl and alkoxy groups; with the proviso that the total number of carbon atoms for R 1 , R 2 and R 3 is at least 6, but preferably at least 8, 9, 10, 11 and in some embodiments at least 12.
  • R 1 , R 2 and R 3 are independently selected from alkyl or alkoxy groups comprising from 1 to 8 carbon atoms with the proviso that the total number of carbon atoms is at least 8.
  • Each alkyl or alkoxy group may independently be: straight (e.g. ethyl, propyl, butyl, pentyl, etc.) or branched (e.g. isopropyl, isobutyl, etc.), and may be unsubstituted or substituted (e.g. substituted with such groups as a hydroxyl).
  • the three alkyl groups (R 1 , R 2 and R 3 ) are independently selected from unsubstituted alkyl groups which may be straight or branched.
  • the three alkyl groups or moieties are selected from: ethyl, propyl, butyl, pentyl, and hexyl moieties.
  • R 1 , R 2 and R 3 are each a n-butyl group, i.e. tri-n-butyl amine.
  • "mixed species" of the subject tertiary amines may be used, or the subject tertiary amines may be used in combination with amines falling outside the definition provided above, e.g. primary and secondary amines, or tertiary amines falling outside the scope of Formula 1.
  • Suitable tertiary amines include those selected from a group consisting of tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri (isooctyl) amine, trimethylamine, triethylamine, tri-n-propylamine, tri-n-butyl amine, and tri (isobutyl) amine.
  • Counterion X - in formula -NR 3 + X - may be any inorganic or organic anion that serves to catalyze the etherification reaction, such as halogens, hydroxides, carboxylates, carbonates, and sulfates.
  • the anion may be monovalent or multivalent.
  • the anion is preferably a halogen, more preferably identical to the halogen in the epihalohydrin.
  • less than all of the monomer units of the crosslinked copolymer are functionalized with ion exchange groups.
  • Most anion exchange resins are prepared in a manner that maximizes degree of functionalization of monomer units, in order to maximize resin dry weight exchange capacity (measured in milliequivalents per gram (meq/g)).
  • the degree of monomer unit functionalization typically is from 80% to less than 100%, and is reduced by incomplete chloromethylation, methylene bridging between monomer units that occurs due to side reaction during the chloromethylation reaction and incomplete amination of the chloromethylated sites or loss of the chloromethylated sites by side reactions during amination (e.g. hydrolysis).
  • degree of monomer functionalization from anion exchange resin dry weight capacity and molecular weight of functionalized and nonfunctionalized comonomers in the anion exchange resin.
  • the degree of monomer unit functionalization ranges from 2% to 60%, preferably from 10% to 40%.
  • dry weight anion exchange capacity is less than 3.5 meq/g, and preferably between 0.5 meq/g and 3.0 meq/g.
  • the anion exchange resins especially gel type anion exchange resins, have an average particle size of 200 micrometers ( ⁇ m) or less.
  • the average particle size is preferably within a range of from 10 ⁇ m to 200 ⁇ m and more preferably from 20 ⁇ m to 100 ⁇ m. This contrasts with conventional anion exchange resins that have an average particle size of from 50 mesh (289 ⁇ m) to 20 mesh (841 ⁇ m) to provide convenient handling and low pressure drop in fixed bed operation.
  • the anion exchange resin may have a broad, narrow or uniform particle size distribution. Narrow or uniform particle size distributions are preferred.
  • the anion exchange resin is prepared using a low amount (0.1 weight percent (wt%) to 4 wt%, based upon total weight of monomers used during copolymer production prior to functionalization) of crosslinking monomer.
  • wt% weight percent
  • most gel-type anion exchange resins are prepared with from 2 wt% to 10 wt % crosslinking monomer and most macroporous anion exchange resins are prepared with from 4 wt% to 10 wt % crosslinking monomer.
  • the polyhydric phenol may be one of a variety of starting materials, including bisphenol-A, bisphenol-F, phenol-formaldehyde novolacs, cresol-formaldehyde novolacs, bisphenol-A-formaldehyde novolacs, trisphenols, biphenols, diphenols, and hydroquinone.
  • Other polyhydric phenols may be found in US Patents 3,372,142 , 4,313,886 , 5.310.955 . and 5,372,790 .
  • Bisphenol-A is an especially preferred polyhydric phenol.
  • the epihalohydrin may be any known epihalohydrin, with epichlorohydrin, epibromohydrin, and methylepichlorohydrin being preferred and epichlorohydrin being more preferred.
  • the inorganic hydroxide may be an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide, or an alkaline earth metal hydroxide such as calcium hydroxide.
  • Sodium hydroxide is a preferred inorganic hydroxide.
  • cosolvents include any solvent that contains an alcohol functionality.
  • suitable aliphatic alcohols include methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-butanol, t-butanol, 2-methyl-2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol and 4-methyl-2-pentanol.
  • suitable alcohol with ether functionalities are 1-methoxy-2-ethanol, 1-ethoxy-2-ethanol, 1-butoxy-2-ethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-isobutoxy-2-propanol, 1-phenoxy-2-propanol, 1-methoxy-2-butanol, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, ethylene glycol monoisopropyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono-n-butyl ether, and ethylene glycol mono-tert-butyl ether.
  • the reaction may also be conducted in the presence of an organic dilution solvent.
  • the dilution solvent may be any solvent which increases solubility of the epoxy resin in the organic phase.
  • the dilution solvent when used, preferably contains no functionalities that react easily with the polyhydric phenol, the epihalohydrin, the alkali metal or alkali earth metal hydroxide, or water.
  • the dilution solvent preferably has limited solubility in water to facilitate brine separation and water washing. Examples of suitable dilution solvents include aromatic hydrocarbons, halogenated hydrocarbons, ketones and ethers.
  • Suitable dilution solvents include, but are not limited to, toluene, xylenes, methyl ethyl ketone and methyl isobutyl ketone. Mixtures of one or more of these solvents may also be used.
  • the etherification reaction is preferably conducted at a temperature between 20 degrees centigrade (°C) and 100 °C, more preferably between 40 °C and 70 °C.
  • the etherification reaction is preferably conducted with an excess of the epihalohydrin, more preferably using from more than 1 mole to 20 moles of the epihalohydrin per mole-equivalent of phenolic hydroxyl (OH) moiety, and most preferably using between 2 moles and 10 moles of epihalohydrin per mole-equivalent of phenolic OH moiety.
  • Replicate CEx 1 but use DowexTM 1X8 anion exchange resin (quaternary trimethylammonium chloride form styrene-divinylbenzene type, gel, 8% divinylbenzene crosslinked, 20 mesh (841 micrometer ( ⁇ m)) to 50 mesh (289 ⁇ m) size (with size determination based on wet resin), total exchange capacity 1.3 meq/ml, dry weight capacity 3.9 meq/g), and stop the reaction after 28 hours.
  • the flask contents show a phenolic OH conversion of only 66%.
  • Replicate CEx 1 but use DowexTM 1X2 anion exchange resin (quaternary trimethylammonium chloride form styrene-divinylbenzene type, gel, 2% divinylbenzene crosslinked, 16 mesh (1 millimeter (mm)) to 100 mesh (149 ⁇ m) size(with size determination based on wet resin), total exchange capacity 0.8 meq/ml, dry weight capacity 4.3 meq/g), and stop the reaction after 23 hours.
  • Fig. 1 shows catalyst activity for Ex 3 (DowexTM 1X2) relative to CEx 1 (DowexTM MSA1) and CEx 2 (DowexTM 1X8).
  • Fig 1 suggests that ion exchange resins with lower crosslinking density (Ex 3 at 2% versus CEx 1 at 6% and CEx 2 at 8%) have higher activity.
  • Replicate Ex 3 but use fine mesh (200 mesh (74 ⁇ m) to 400 mesh (37 ⁇ m)) (with size determination based on wet resin) DowexTM 1X2 anion exchange resin and stop the reaction after 7 hours.
  • Fig. 2 compares catalyst activity of this Ex 4 with Ex 3 and suggests that gel-type ion exchange resins with smaller particle size of Ex 4 have higher activity than the larger particle size resin of the same type used in Ex 3.
  • CEx 6 flask contents show a phenolic OH conversion of only 68%, a value low enough to make determination of oligomer content of little use.
  • the flask contents analysis suggest that the catalyst of Ex 5, with a crosslinking monomer content of 4%, is more active than that of CEx 6, with a higher crosslinking monomer content of 8%.
  • Ex 4 above, with a crosslinking monomer content of 2% is even more active than Ex 5.
  • Replicate CEx 1 but use quaternary trimethylammonium chloride macroporous anion exchange resins described in Table 1, which may be prepared by copolymer production methods similar to those described in US 5,663,455 (with a divinyl benzene content of 3 wt% and use of 47 wt% of a porogen, an organic solvent in which mononmers, but not the copolymers, are soluble), chloromethylation techniques which use control of temperature and time to control extent of chloromethylation (such as described in Helfferich, Ion. Exchange, McGraw-Hill, 1962, p.52 and Dorfner, Ion Exchangers, Walter de Gruyter, 1991, p.
  • Fig. 5 compares activities of the catalysts (Ex 10-13). Table 2 below summarizes oligomer content of reaction products for each catalyst (Ex 10-13). Fig. 5 and the results summarized in Table 2 demonstrate that partially functionalized anion exchange resins with lower dry weight capacity (Ex 11-13) have higher activity and generate a product with lower oligomer content than fully functionalized anion exchange resins (Ex 10).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Epoxy Resins (AREA)
  • Epoxy Compounds (AREA)
EP10798211.8A 2009-12-16 2010-12-07 Production of epoxy resins using improved ion exchange resin catalysts Not-in-force EP2513184B1 (en)

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US28684709P 2009-12-16 2009-12-16
PCT/US2010/059177 WO2011084304A1 (en) 2009-12-16 2010-12-07 Production of epoxy resins using improved ion exchange resin catalysts

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EP2513184A1 EP2513184A1 (en) 2012-10-24
EP2513184B1 true EP2513184B1 (en) 2014-06-25

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US (1) US8742055B2 (ja)
EP (1) EP2513184B1 (ja)
JP (1) JP5764140B2 (ja)
KR (1) KR20120103644A (ja)
CN (1) CN102753597B (ja)
BR (1) BR112012014237A2 (ja)
TW (2) TW201609849A (ja)
WO (1) WO2011084304A1 (ja)

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EP2773682A4 (en) * 2011-11-01 2015-04-29 Dow Global Technologies Llc LIQUID EPOXY RESIN FORMULATIONS

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US3176027A (en) 1965-03-30 Process for the production of glycide ethers of monohydric phenols
NL302360A (ja) 1959-03-13
US3372142A (en) 1964-01-31 1968-03-05 Dow Chemical Co Epoxidation process
CH463528A (de) 1966-06-06 1968-10-15 Ciba Geigy Verfahren zur Herstellung von Glycidyläthern von Polyphenolen mit hohem Epoxydsauerstoffgehalt
SE7411007L (ja) 1973-10-10 1975-04-11 Ciba Geigy Ag
US4341658A (en) 1980-04-10 1982-07-27 The Dow Chemical Co. Catalyst for reacting phenolic hydroxyl groups with epoxy groups
US4276406A (en) 1980-04-10 1981-06-30 The Dow Chemical Company Catalyst for reacting phenolic hydroxyl groups with epoxy groups
US4313886A (en) 1980-09-25 1982-02-02 The Dow Chemical Company Process for preparing liquid epoxy resins
ES2061128T3 (es) * 1990-07-20 1994-12-01 Dow Chemical Co Procedimiento para producir en continuo productos de reaccion.
US5372790A (en) 1991-01-18 1994-12-13 The Dow Chemical Company Vertical continuous reactor
US5663455A (en) 1995-10-12 1997-09-02 The Dow Chemical Company Process for conducting etherification reactions using as catalysts strong-acid, cation-exchange resins prepared under high temperature conditions
KR20050052484A (ko) 1997-03-17 2005-06-02 마츠시타 덴끼 산교 가부시키가이샤 데이터 처리방법
CN100473159C (zh) 1997-03-17 2009-03-25 松下电器产业株式会社 发送和接收动态图像数据的方法
CN1546548A (zh) 2003-12-03 2004-11-17 青岛帝科精细化学有限公司 一种合成高纯低分子双酚a环氧树脂的工艺
CN100532418C (zh) 2006-09-26 2009-08-26 蓝星化工新材料股份有限公司无锡树脂厂 采用阴离子催化剂合成环氧树脂的方法
CN104710597A (zh) * 2008-03-25 2015-06-17 陶氏环球技术有限责任公司 制备液体环氧树脂的方法

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TW201609849A (zh) 2016-03-16
CN102753597B (zh) 2014-12-17
US20120283453A1 (en) 2012-11-08
BR112012014237A2 (pt) 2016-06-14
EP2513184A1 (en) 2012-10-24
TW201124440A (en) 2011-07-16
KR20120103644A (ko) 2012-09-19
US8742055B2 (en) 2014-06-03
JP2013514434A (ja) 2013-04-25
JP5764140B2 (ja) 2015-08-12
CN102753597A (zh) 2012-10-24
TWI500647B (zh) 2015-09-21
WO2011084304A1 (en) 2011-07-14

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